Light-sensitive layers



Q Patented Mar. 21, 1939 UNITED STATES HGHT- SENSITIVE LAYERS Maximilian Paul Schmidt, cum sin. and Georg Werner, Wlecbaden-Biebrloh, Germany,

ore to Kalle & o. .Aktiengesellsohaft,

Wiesbaden-Biebrlch, Germany No Drawing. Application November 6, 1986, Se-

?rslsNo. 109,550. In Germany November 14,

9Ciaims.

The present invention relates to improved light-sensitive layers.

Only a few groups of diam-compounds have proved suitable for use in the diazo-type process.

At the present time the oxyand aminodiazocompounds or their substitution products are the most important. Only a few diam-compounds of these last named groups have found practical application since the properties required of the 0 light-sensitive layers and pictures produced therefrom have become greater. Inaddition to the durability and light-sensitivity of the layers containing the diazo-compounds there is still a desire for durability, insensitivity to acid and 5 fastness to light in the finished diazo-type print. The diam-compounds must be as strongly colored as possible so that the progress of the copying process can be easily followed. Furthermore they must lead to the production of certain tones,

particularly dark brown and black shades. The

several diam-compounds at present known exhibit the various desired properties in a varying degree, so that for each purpose one or the other of the diazo-compounds is selected and in practice a large number of these diazo-compounds is used; however, this number still needs to be increased. Y

According to this invention, diazocompounds are employed for the production of light-sensitive layers which diazo compounds have a hydro:

genated ring fused with the benzene nucleus containing the diazo group wherein the said hydrogenated ring consists of at least tour carbon atoms and one tertiary amino group having its nitrogen atom in the said hydrogenated ring.

For example, by using diazo compounds of hydrogenated quinolines which have a substituent attached to the nitrogen of the hydrogenated ring, highly sensitive strongly colored layers are produced which, in combination with the usual azo components, give pictures in dark lines. This is surprising, since the non-hydrogenated aminoquinolines yield diazo compounds which are un- 45 suitable for the diazo-type process, because they are decomposable, notcapable of being completely bleached and of disadvantageous shade. The diazo compounds of. hydrogenated indoles and carbazoles which have a substituent attached to the nitrogen of the hydrogenated ring, for instance, alkyl or aralkyl, behave similarly to the hydrogenated diam-quinolines.

The compounds which are employed accord- 55 ing to the invention have a substituent attached to the nitrogen of the hydrogenized ring, for instance, alkyl or aralkyl. Preferably compounds are used in which the diazo-group is in paraposition to the nitrogen of the hydrogenized ring.

0 The nucleus containing the diazo-group may also contain substituents, for instance halogen, alkoxy-groups or the like. The amines which serve asparent materials for the new diamocompounds may be made by known methods. Advantageously they are produced by coupling the hydrogenized quinoline, indole or carbazole with a diam-compound, for example diazotized sulphanilic acid, and then reducing the dyestufi produced. The hydrogenized amines obtained in this manner are then further diatotized by any known process.

The diazo-compound may be applied alone or together with an azo-component. There'may be added to the layers and pictures metal salts,

thiourea and other additions which have hitherto been used in the diam-type process. The picture is developed in known manner by a vapor, for example ammonia or steam or by a developing solution, depending upon whether the diazocompound exists in the layer alone or together with an azo-component, and if desired in presence of alkali or a substance of alkaline action.

The following examples illustrate the invention:

1. 35 grams of the zinc chloride double salt of the diam-compound from 2':6'-dichloro-N- benzyl-l 2 3 4-tetrahydr0- 6-amlnoquino1ine, obtainable from tetrahydroquinoline (Ber. 16, page 728) C Cl ' by reaction with dichlorobenzylchloride (boiling Grams 10 10 40 40 10 Tartaric acid Boric a Thiour 1:3:6-naphthalene-trisulphonic acid Ammonium sulphate Aluminium sulphate in 1 liter ofwater and the solution is brushed on O-aminoquinolinea which paper. The prints obtained by exposing the layer are developed with a solution of inlliterofwater.

Blue-black line prints are produced. Instead of the diam-compound from 2':6'-dichloro-N- benayl-c-aminotetrahydroquinoline the dialoirom N-bensyl-d-aminotetrahydroquinoline may be used.

2. 81 grams of the tin chloride double salt of the diam-compound from N-bensyl-1z2z3z4-tet- I'lhldm-S-m-B-aminoquinollne are dissolved in 1 liter of water and tosether with the additions named in Example 1 and prints obtained-as usual. By developing with the developer prescribed in Example 1 black-blue lines are obtained.

Instead oi the aforesaid diam-compound the unds i'rom N-benzyl-1:2:8:4- tetrahydno-S-oxy-tmethyl 8 aminoquinoline, N- bmryl-lziztz4-tetrahyro-3-oxy-5-chloro-6- aminoquinoline, N-bensyl-l :2 8 :4-tetrahydro-3-oxy- B-ethoxy-d-aminoquinoline or 2':6'-dichloro-N- banal-1:3:3z4-tetrahydro-8-oxy- 6 aminoquinoline may be used.

According to the speed of coupling exhibited by these diam-components it is advantageous to vary the proportion of the alkali in the developer prescribed in Example 1. In this manher deep dark tones can be obtained in every case. The diam-compounds named in this Example may be made by coupling the corresponding 1:2:3z4-tetrahvdro-3-oxyquinoline with dialotined sulphanilic acid and reducing the arcdyeatufl to the corresponding tetrahydro-S-oxymaythenbedi zotised' intheusualmanner.

In casu in which coupling with dianobennene sulphonic acid don not occur the amino-group maybeintroducedbywayotthenitrosocompound.

3. A solution 01' 31 grams of the tin chloride double salt of thediaso-compound from N-benaoyl-1:2:8:4-tetrahydro-8 aminoquinoline are dissolved in 1 liter of 'water together with the additions named in Example 1 and the solution is applied to paper. velopment are in deep brown lines.

The diam-compound is made by starting with tetrahydroquinoline and converting this into the bsnaoyl compound by nitrating in glacial acetic acid with nitric acid (specific sravity==1.41) there is obtained a well-crystallized nitro-body from which the amino-compound is produced by reducing with zinc dust and alcoholic hydrochloric acid. The amino-compound may be dinoticed in the usual manner.- Instead of the diam-compound from N-benzoyl-tetrahydroaminoquinoline that from N-bensoyl-1:2:3:4-tetra-. hydro-:8diethoxy-6-aminoquinoline may be used. It can be made from the 1-amino-2z5- diethoxybensene by ring condensation by the Straup method (Ber. 14, page 1002), hydrogenating and iinally nitrating the benzoylated product, reduction and dianotization.

4. 31 grams or the tin chloride double salt of the diam-compound from N-benzyl-1z2z3z4- tetrahydro-S-on-G aminoquinoline are dissolved together with the equivalent quantity of- R-aaltandthemixtureisbrushedonpaper.

The prints obtained on de- H. Km 8 Ha I The print may be developed with the developer named in Example 1, whereby black-brown lines are obtained.

6. In 1 liter of water are dissolved Grams Citric acid 10 Boric aci 10 Thiourea i 40 Naphthalene-1:3:8-trisulphonic acid 40 Ammonium sulphate 20 Double salt of zinc chloride and the discocompound from 5-amino-2-methyl-N- 2 :6'- dichlorobenzyl 2:3 dihydroindole and applied to paper 34.2 a

As a developer !or this paper there maybe used a solution containing in 1 liter of water Grams Sodium carbonate 10 Trlsodium phosphate 40 Borax 20 Sodium thiosulphate 80 Dihydro-reaorcino1 2 Phloroglucinol, anhydrous 3.6

In this manner brown line prints are obtained.

7. Instead of the diasommpound used in Example 6 34.8 grams of the tin chloride double salt of the diam-compound from 5-amino-2 :8- dimethyl-N-benzyl-2:3-dihydroindole are used; with the same developer as is prescribed in Example 1 more black-brown tones are obtained.

8. In 1 liter oi! water are dissolved Grams 'Iartaric a i Boric acid It Thiourea 40 1:3:6-naphthalenetrisulphonic acid 40 Ammonium sulphate 5 Sodium sulphate 5 Aluminium sulphate 15 Phloroglucinol, anhydrous 3.8 Orsin 2.0

Chloro-tin double salt of the diam-compound .irom G-amino-Q-ethylhelahydrocarbamle 3g ries and hydrocarbazole series are obtainable from the hydroindoles or hydrocarbazoles, respectively, which can be made in the known manner by suitable reduction, (for example, with tin and hydrochloric acid) of the indoles or carbazoles, respectively. The obtained compounds are alkylated or aralkylated and then further converted, as described in Example 2.

We claim:

1. A light sensitive layer comprising as the light sensitive substance a diam compound of a substance selected from the group consisting of tertiary hydrogenized quinolines, tertiary hydrogenized indoles and tertiary hydrogenized carbazoles.

2. A light sensitive layer comprising as light sensitive substance the dlazo-compound from 2' :6'-dichloro-N-benzyl-1:2:3:4- tetrahydro 6 alminoquinoline.

3. A light sensitive layer comprising as light sensitive substance the diazo-compound from N-benzyl-l:2:3:-i-tetrahydro-3 oxy 6 aminoquinoline.

4. A light sensitive layer comprising as the light sensitive substance a diam-compound which has a hydrogenated ring fused with the benzene nucleus containing the diazo-group wherein the said hydrogenated ring consists of at least four carbon atoms and one tertiary amino group having its nitrogen atom in the ring.

5. A light sensitive layer comprising as the light sensitive substance a diam-compound which has a hydrogenated ring fused with the benzene nucleus containing the diam-group wherein the said hydrogenated ring consists t at least four carbon atoms and one tertiary amino group having its nitrogen atom in the ring and attached to the said benzene nucleus in para-position to the said diam-group.

6. A light sensitive layer comprising as the light sensitive substance a diazo-compound which has a hydrogenated ring fused with the benzene nucleus containing the diazo-group wherein the said hydrogenated ring consists of at least four carbon atoms and one nitrogen atom which latter carries a benzyl residue as substituent and is attached to the said benzene nucleus in para-position to the said diazo-group.

'7. A light sensitive layer comprising as the light sensitive substance a diam-compound which has a hydrogenated ring fused with the benzene nucleus containing the diazo-group, the said hydrogenated ring consisting of at least four carbon atoms and one tertiary amino group having its nitrogen atom in the ring and attached to the said benzene nucleus in para-position to the said diazo-group wherein the said benzene nucleus carries two alkoxy groups in 5- and 8- positions as substituents.

8. A light sensitive layer, according to claim 1, wherein the diazo-group of the said diazo-compound stands in para-position to the nitrogen atom or the hydrogenated ring.

9. A light sensitive layer comprising as light sensitive substance the diam-compound from N-benzoyl-l :2 :3z4-tetrahydro-5z8- cliethoxy 6 aminoquinoline.

Maximum PAUL scmsm'r. OSKAR sits. GEORG- mm. 

